CN1933920A - Painting device, painting method, and display member provided therefrom - Google Patents

Painting device, painting method, and display member provided therefrom Download PDF

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Publication number
CN1933920A
CN1933920A CN200580009576.3A CN200580009576A CN1933920A CN 1933920 A CN1933920 A CN 1933920A CN 200580009576 A CN200580009576 A CN 200580009576A CN 1933920 A CN1933920 A CN 1933920A
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CN
China
Prior art keywords
coating
component
fluctuation
coating unit
discharge
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Pending
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CN200580009576.3A
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Chinese (zh)
Inventor
梶野佳范
小林裕史
铃木哲男
久保善彦
和田修
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Toray Industries Inc
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Toray Industries Inc
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Publication of CN1933920A publication Critical patent/CN1933920A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/10—Storage, supply or control of liquid or other fluent material; Recovery of excess liquid or other fluent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
    • B05C5/0254—Coating heads with slot-shaped outlet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography

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  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Apparatus (AREA)

Abstract

A painting device, a painting method, and a display member provided by the device and the method. In the painting device and the painting method capable of suppressing discharge pulsation, providing thin-film coating having excellent film thick uniformity, and having excellent discharge responsiveness, a member (portion 5) damping the discharge pulsation is installed between a paint liquid supply means (for example, syringe pump 3) and a painting means (for example, die ferrule 6). The discharge pulsation generated by the syringe pump is damped by the volumetric change of the member (5a) damping the pulsation which is disposed in the pulsation damping portion (5), and a constant volume of discharge with suppressed pulsation can be provided from the die ferrule.

Description

Coating unit, coating method and thus gained display unit
Technical field
The present invention relates to a kind of coating units, more particularly to a kind of coating unit suitable for intermittent application, it is additionally related to use the coating method of the coating unit, a kind of the discharges fluctuation for excluding coating fluid as far as possible is provided to prevent the film thickness being induced by it variation, even and the coating discharge responsiveness of interval is also good coating unit.Coating unit of the invention can also suitably be used in display equipment, display equipment colour filter, LCD array, optical light filter in addition to being suitable for other than the case where being equably coated with the film of magnetic substance or film etc. on the substrate thin slice or glass.
Background technique
In recent years, in the manufacturing engineering of recording medium etc., it is desirable that be equably coated with the film of magnetic substance or coating etc. on the matrixes such as thin slice, therefore create various discharges for making masking liquid as far as possible and fluctuate reduced infusion device.
The field most suitably used as its, optical light filter plastic base, the glass substrate of liquid crystal display, colour filter glass substrate etc. in, the highly desirable thin layer on the smaller substrate that coated length is discontented with 2m and be equably coated with the technologies of various coating.
As industrial such method for forming film on substrate, using by coated part, one by one to coating machine supply, monolithic coating method supply coating coating, transported to the subsequent processings such as dry, roll-type cladding process, bar coating method, mold (ダ イ) cladding process were widely applied as monolithic coating method in the past.
Roll-type cladding process is method masking liquid copied to by the roller of rubber roller etc. on substrate, can carry out the coated part to long size, cylinder shape the coated part rolled coating, but since masking liquid is by sequentially from liquid device is contained to application roller, the relationship of substrate conveying, the time that masking liquid is exposed to air is long, it is not only easy to produce and goes bad due to caused by the moisture absorption of masking liquid, be also easy to generate being mixed into for foreign matter.In addition, film thickness variation can also become larger, therefore not applicable with highly viscous masking liquid or when carrying out the coating of thick film.
Bar coating method is used in the method that the stick that lametta is wrapped around on bar is coated with masking liquid on substrate, in the method, metal wire due to being wound in bar is directly contacted with substrate, so having the shortcomings that homogenization is poor, the trace of kish line is such in the case where masking liquid is non-Newtonian or viscosity is high.
Mold cladding process is widely used to the coating of thick film all the time or is continuously coated with the purposes of highly viscous coating.In use die coater in the case where forming film on being coated part, it is known that the coating methods such as showering curtain type cladding process, extrusion molding, liquid pearl method (one De method of ビ).Usually, in the state of making the nozzle of die coater approach coated part, from the slit discharge coating for being set to nozzle, the coating drop for being known as coating bead is formed between the nozzle and the coated part relatively moved with keeping certain intervals with it, draws coating with the movement of coated part in this state to form film.Also, if using by from slit for give as film formed consumed by coating same amount coating to being continuously formed liquid pearl method as film, being formed by film can be with the uniformity of very high precision realization film thickness.
Therefore in recent years, the application for using die coater in the intermittent application for requiring film thickness uniformity, and having created the various manufactures to colour filter etc. is proposed.
But, in above-mentioned previous method, although can be by making to ensure the uniformity of certain film thickness and applying liquid supplying device precise treatment, but the influence of vibration due to applying liquid supplying device and other driving portions etc., fluctuation is generated on the discharge of die nozzle, so that masking liquid pearl minutely vibrates and can generate periodically uneven or irregular unevenness.In recent years, it especially in the field of display body purposes, even extremely small film thickness, which changes, can also be found as display unevenness by vision, is affected to quality, therefore have the tendency that the requirement for applying film uniformity is increasingly increased.
In order to obtain more uniform film by using the method for die coater, need to pursue the limit for applying film uniformity, so needing to completely remove discharge fluctuation and vibration small as caused by the vibration of infusion device, the non-uniform movement for wiping dynamic portion, vibration of transfer line etc..
Generally as the method for the influence for removing the discharge fluctuation generated by infusion device, the scheme of the setting accumulators such as air chamber or air storage chamber is usually proposed.
But in the construction of the setting sealed chambers such as air chamber, due to masking liquid retentate portion mostly thus it is unfavorable to masking liquid apt to deteriorate, in addition, the problem of having due to air is contacted with masking liquid and generates rotten and dissolution.In storage die mould air storage chamber, the pressure that spues is absorbed using accumulator when painting work starts, to lead to the problem of masking liquid discharge delay, in addition, when being noted painting work stopping spue can certain time until the pressure for being trapped in accumulator releases such responsiveness it is bad.That is, the accumulator when carrying out intermittent application is difficult to carry out uniform film formation (referring for example to Patent Document 1).
In addition, the schemes (referring for example to Patent Document 2, Patent Document 3) of various foaming elastomers is configured in pipeline as the component of buffering fluctuation although proposing, there is can from the foaming body of setting in a liquid into liquid leadage air or since liquid immersion leads to problems such as its elastic property lose too early into foaming body.About this point, although it is contemplated that by the method etc. of foaming elastomer covering coating, but in the case where covering material and elastomer are in adhering state, the volume of elastomer is changed to be hindered by the bonding plane of itself and covering material, its elastic property damage, although the variation that can respond big pressure is highly difficult for the buffering of minor fluctuations.In addition, though covering material and elastomer be in close contact state not be bonding state in the case where, because can due to internal elastomeric volume change and generate the separation with covering material, therefore new secondary vibration can be generated, or fold or necking down are generated in covering material, so these to extremely small fluctuation buffered with also becoming the vibration cause that cannot ignore on the way.That is, the device buffered to the pressure oscillation of fluid considered, it is uneven with small film thickness required on the way to have not been reached yet the degree that can improve small film thickness unevenness, especially display equipment etc. in the past；In addition, the buffering effect and discharge responsiveness of discharge fluctuation cannot be satisfactory to both parties, so not can solve the formation of the extremely uniform film in intermittent application.
Patent Document 1: Japanese Unexamined Patent Publication 10-159803 bulletin
Patent Document 2: Japanese Unexamined Patent Publication 2000-18202 bulletin
Patent Document 3: Japanese Unexamined Patent Publication 2002-61788 bulletin
Summary of the invention
The present invention is completed for solving this previous technical task, and its purpose is to provide a kind of coating units of good film coating of available film thickness uniformity without the fluctuation that spues.And then it also resides in and a kind of good high-precision intermittent application device of discharge responsiveness and coating method is provided.
In order to solve such project, the present invention has construction below.I.e.
(1) a kind of coating unit, at least have and applies liquid supplying device and masking liquid is coated on the coating unit on basis material, they are connected by pipeline, masking liquid is coated on basis material, it is characterized in that, it is reached anywhere in the pressure generated by the painting liquid supplying device, is spued the component of fluctuation configured with buffering, the spue component of fluctuation of above-mentioned buffering is at least by being enclosed internal gas and enclosing the component that the material of the gas constitutes.
(2) coating unit as described in above-mentioned (1), which is characterized in that the component of above-mentioned buffering discharge fluctuation regards below specific gravity is the half of the actual specific gravity of the material of above-mentioned enclosed gas.
(3) coating unit as described in above-mentioned (1) or (2), 60% or more of the surface area for soaking the component that area (area being in contact with liquid) is buffering discharge fluctuation of the component of fluctuation it is characterized in that, above-mentioned buffering spues.
(4) such as the described in any item coating units in above-mentioned (1)~(3), which is characterized in that the collapsibility Index A of the component of above-mentioned buffering discharge fluctuation indicated with following formula (1) is 1.4~20.
A=S/ (4.84 × V2/3)    (1)
Wherein, S indicates that the spue component of fluctuation of above-mentioned buffering under 25 DEG C, 1 atmospheric pressure with masking liquid soaks area (cm2), V indicates the volume V (cm of the component of buffering discharge fluctuation under the above conditions3)。
(5) coating unit as described in any one of above-mentioned (1)~(4), which is characterized in that oxygen permeability of the material of above-mentioned enclosed gas under conditions of 40 DEG C, 90%RH is 2500cm3/m2DayMPa or less.
(6) such as the described in any item coating units in above-mentioned (1)~(5), which is characterized in that use mold cladding process as the method that masking liquid is coated on to basis material.
(7) such as the described in any item coating units in above-mentioned (1)~(6), it is characterized in that, with the device for further increasing the pipeline internal pressure generated by painting liquid supplying device, by the arrangement increases the components that the section of pipeline internal pressure configures above-mentioned buffering discharge fluctuation.
(8) such as the described in any item coating units in above-mentioned (1)~(7), which is characterized in that at least pumped using piston type quantitative as liquid supplying device is applied.
(9) coating unit as described in above-mentioned (8), which is characterized in that the discharge-amount Q of each second of the masking liquid to spue from coating unit is 0.1~20cm3。
(10) coating unit as described in above-mentioned (8) or (9), which is characterized in that volume V (cm of the component of above-mentioned buffering discharge fluctuation under 25 DEG C, 1 atmospheric pressure3) and from coating unit spue masking liquid discharge-amount Q (cm per second3) meet following formula (2).
0.05≤V/Q≤2    (2)
(11) such as described in any item coating units of above-mentioned (8)~(10), which is characterized in that the device of the rising movement for the pipeline internal pressure that there is measurement to spue when starting.
(12) masking liquid is coated on basis material using coating unit described in any one of above-mentioned (1)~(11) by a kind of coating method.
(13) a kind of manufacturing method of colour filter, the process including using coating method described in above-mentioned (12) to be coated.
(14) a kind of manufacturing method of LCD array substrate, the process including using coating method described in above-mentioned (12) to be coated.
(15) a kind of display equipment, which is characterized in that use and utilize the resulting colour filter of method or LCD array substrate described in above-mentioned (13) either (14).
Using the present invention, the influence for the fluctuation that spues can be reduced, the high film coating of film thickness uniformity is stably obtained, is especially very suitable for the case where intermittently being coated to basis material.
In addition, being configured at the component of the buffering discharge fluctuation in the pressure pipeline in the case where rising the internal pressure in masking liquid pipeline, since the responsiveness of its volume change improves, so discharge fluctuation can be buffered, and discharge responsiveness is high, more effectively so as to more improve film thickness uniformity.Also, in the case where the device of the pipeline internal pressure when having measurement to spue, the deterioration of the component of buffering fluctuation can detecte, so as to become the higher apparatus for coating of productivity.
Detailed description of the invention
Fig. 1 shows one of the die coating formula coating unit of the component with buffering fluctuation of the invention
The flow chart of embodiment.
Fig. 2 indicates the flow chart of the component for the buffering fluctuation for having of the invention and one embodiment of pipeline internal pressure riser and the die coating formula coating unit of component degradation function.
Fig. 3 indicates to have used the flow chart of one embodiment of the coating of previous die coater.
Fig. 4 indicates the flow chart that well known air cell type accumulator is combined in one embodiment of the coating of die coater formula obtained from previous die coater.
The film thickness measuring result of Fig. 5 embodiment 1,2.
The film thickness measuring result of Fig. 6 embodiment 5.
The film thickness measuring result of Fig. 7 Comparative Examples 1 and 2.
The film thickness measuring result of Fig. 8 comparative example 3,4.
Label declaration
1 applies 2 Attractive side switching valve of flow container
3 hydraulic pump, 4 exhaust end switching valve
The component of 5 fluctuation buffer locations 5a buffering discharge fluctuations
6 die nozzle, 7 basis material
8 workbench, 9 pressure gauge
10 pipeline internal pressure riser, 11 control unit sequence controller
12 pump 13 air cell type accumulators of driving circuit
C1 motor drive signal S2 pressure gauge setting pressure arriving signal
Specific embodiment
It is exemplified below specific example and illustrates a specific embodiment of the invention, but the present invention is not only defined in the specific example in this measure.
Coating unit of the invention can be adapted for requiring the uniformity of film thickness, such coating method for requiring very high precision must be treated in the discharge fluctuation of masking liquid as problem.Mold cladding process, roll-type cladding process, bar coating method etc. can be listed as such coating method.
The present invention can also be used in the case where carrying out and being continuously coated with, but since responsiveness is good so can play very excellent characteristic in the case where being intermittently coated.The difference of continuous coating and the coating of interval is: the basis material that the former uses is usually long size, coating method is improper coating position before coating film reaches when normal (stabilizations) coats state not finished product in principle, and utilize the part normally coated, in contrast, the latter distinguishes as coating method below, that is: the coating method stopped comprising 1 time to multiple coating on a basis material, or using the basis material of monolithic type as representative, the coating method that will be utilized from coating initial stage to all sites of coating terminal as 1 finished product unit, or the coating method implemented on several meters of basis materials below below several minutes or to the painting cloth length of 1 basis material in the coating time to 1 basis material.
The present invention is to lower the influence for the fluctuation that spues to obtain the coating unit of uniform film, more particularly to a kind of technology of device that can be adapted for intermittently being coated.Painting liquid supplying device is the device that masking liquid is output to coating unit used in coating unit of the invention, it can be cited for example that the various power machines such as gear pump, diaphragm pump, tube pump, CT pump (manufacture of Coaxial Tubephragm Pump U ガ ネ イ society), snakelike pump, reciprocating pump.These devices can be used alone, and can also be used with multiple combinations.In the present invention, it is preferred to piston type quantitative pump excellent using quantitative responsiveness, that uniform film thickness can be obtained.
As the method coated using coating unit of the invention, it is formed on the basis material of rectangle on this aspect of uniform film, it is applicable in roll-type cladding process, bar coating method, mold cladding process, but foreign matter may be mixed into due to masking liquid with roll-type cladding process and bar coating method or be exposed in air and generate the rotten of masking liquid, moisture absorption, in addition, since in highly viscous masking liquid and thick film coating, film thickness uniformity is good, it is advantageous to mold cladding process.In the mold cladding process, die nozzle is generally used as coating unit.Shape as die nozzle; it is set as considering the slit gap of the crushing of the viscosity of masking liquid and discharge slit; slit width is determined by the size and coating width of coated substrates material; manifold shapes inside die nozzle are T shape mould or clothes rack shape etc., try to obtain and uniformly spue on slit width direction.In addition, can be to the masking liquid of manifold portion injection path can also be divided into several places at 1.
Next it is used as specific example, the coating unit for enumerating a kind of die coater of hydraulic pump used as piston type quantitative pump illustrates in further detail.Certainly the present invention is not limited to this patterns.
Fig. 1 is the infusion flow chart of an example for indicating individual coating unit as an embodiment of the invention, illustrates the flowing from masking liquid storage tank to die nozzle.The Attractive side switching valve 2 for being set to and applying 1 downstream of flow container is opened, the attraction of masking liquid the hydraulic pump (applying liquid supplying device) 3 in the downstream by being set to Attractive side switching valve 2.Exhaust end switching valve 4 is closed in this state.
Attract the masking liquid of specified amount to close Attractive side switching valve 2 later, opened the exhaust end switching valve 4 for being set to the downstream of hydraulic pump 3, starts the infusion of hydraulic pump 3.The drop (liquid pearl) of masking liquid is formed between the coated part 7 on workbench 8 and die nozzle 6 by the action, later by making workbench 8 relatively move to form film relative to nozzle 6.Workbench 8 is moved to required coated area or closes exhaust end switching valve 4 before this, to terminate to coat.
In the present invention, in the pattern of Fig. 1, the position 5 of component of the setting configured with buffering discharge fluctuation between hydraulic pump 3 to nozzle 6, wherein being configured with the component 5a of buffering fluctuation.When the discharge program by hydraulic pump 3, since the pressure loss of transfer line and nozzle slot is many to which pipeline internal pressure rises, become the fluctuation of pipeline internal pressure by the discharge fluctuation of the generations such as painting liquid supplying device.The main reason for pressure oscillation is the thickness variation of film, but due to buffering the component buffers fluctuated the influence that spues in masking liquid pipeline, so the fluctuation that spues homogenizes, so as to obtain the uniform coating that no film thickness changes.
In above-mentioned example, the component 5a of buffering discharge fluctuation is provided in path between hydraulic pump 3 and nozzle 6, but the room that branch pipe and being arranged is sealed with the component of above-mentioned buffering fluctuation can also be set in the path, although somewhat difficult in engineering technology, in hydraulic pump or in nozzle configuration buffering spue the component of fluctuation can also be with.
The so-called component for buffering discharge fluctuation of the invention, preferably have the function of that the variation by the pipeline internal pressure generated by the fluctuation to spue absorbs mitigation by the volume change of component, thus the component for homogenizing pipeline internal pressure, it as in order to play property necessary to this effect, can enumerate: absorb vibration and impact；The fast response time of the volume change as caused by the variation of external pressure；Masking liquid and the component both sides of buffering discharge fluctuation will not be made to generate material variation due to contact masking liquid etc.；Flexibility will not be damaged by being buffered the density of component of the fluctuation that spues is got higher even if due to pressurization；Volume will not be vibrated when changing；Will not be plastically deformed Repeated Compression etc..
As the component with such property, the gas by enclosing inside is used in the present invention and encloses the component that the material of the gas is constituted.The component constituted by using the gas of enclosed inside with the material for enclosing the gas, with method other than the above, such as it is compared using the case where foaming elastomers such as the polymer systems such as acrylic rubber, polyurethane rubber, silicone rubber, isobutene rubber, natural rubber, fluorubber elastic material and elastomer gel, the available good volume change of responsiveness for faint pressure oscillation, even the Repeated Compression in intermittent application will not be plastically deformed, so as to be used continuously for a long time.
In addition, with gas is directly configured compared in the method in masking liquid pipeline, will not lead to the problem of it is as follows, i.e., due to masking liquid contacts gas and go bad, due to infusion vibration and fine gas bubblesization are dissolved in masking liquid to which gas outflow becomes coating disadvantage, gas and generate the problems such as timeliness changes without being able to maintain constant gas volume to fluctuate buffering effect.Be formed as bag-shaped for gas is enclosed especially by with the material of the small low-permeability of distortional stress, the responsiveness of the available volume change to external pressure is good, the component of stable shape can be maintained in fluid.
As such for enclosing the material of gas, polyethylene, polypropylene, polyester, polyvinyl alcohol, polyvinyl chloride, poly- 1 can be enumerated, polymer systems elastic material such as the general-purpose plastics such as 1 dichloroethylene thin slice and lactoprene, polyether urethanes, silicone rubber, isobutene rubber, natural rubber, other fluorubber etc..If compromising the responsiveness of the volume change for the gas being enclosed because of the rigidity of the material for enclosing gas, the buffering effect of enough fluctuations may not be able to then be played, so surface hardness when preferably under normal pressure enclosing gas is 70 or less Shore C hardness, when in order to buffer fainter fluctuation, 50 materials below are preferred, as long as the material of the enclosed volume change for not hindering gas in this way, whether consistent with pipeline internal pressure no matter the enclosed pressure of gas, which be set as, is ok.Also, the Shore C hardness illustrated in the present invention is the value acquired by the C hardometer of macromolecule metrical instrument Co. Ltd. system ASKER (registered trademark).In addition, the buffering spues, the half of the actual specific gravity of the material depending on preferably enclosing the gas in specific gravity of the component of fluctuation is hereinafter, more preferably a quarter is hereinafter, still more preferably from 1/6th or less.Lower limit is not particularly limited, but the block of the gas by enclosing if too small is impaired, and it is advantageous to the degree for that can maintain above-mentioned gas barrier.Herein, the buffering spue fluctuation component regard specific gravity as, by all part qualities of buffering discharge fluctuation divided by the value of the volume of above-mentioned component entirety, the actual specific gravity of the material of enclosed gas be the material monomer after the enclosed gas for eliminating internal gas quality divided by above-mentioned material monomer volume value.
In turn, the desirable properties that should have as the material of above-mentioned enclosed gas, can enumerate has low-permeability, and the solvent resistance etc. to masking liquid to liquid (masking liquid ingredient) and gas.If pressurizeing to the component for the buffering fluctuation for having enclosed gas, it then may be different due to enclosing the material of material, masking liquid is possible to penetrate into the inside of the material, or enclosed gas is permeated and is oozed out to outside in turn, damage fluctuation buffering effect, so the preferably high enclosed material of using gas block as far as possible.Such as, in the case where enclosed gas uses air, the nitrogen of the main component as air and the permeability of oxygen must be taken into consideration, if in addition for the purpose of the high coating unit of productivity, the continuous use at least more than a few houres must be taken into consideration, so the material of above-mentioned enclosed gas, it is preferred to use oxygen permeability is 2500cm under conditions of 40 DEG C, 90% relative humidity3/m2DayMPa material below, although and describe afterwards, it the use of oxygen permeability is more preferably 30cm if considering the use due to the case where pipeline internal pressure gets higher and adds high pressure to the material of enclosed gas and longer-term3/m2DayMPa material below.
The thin slice or the high thin slice of solvent resistance for implementing metal evaporation processing to surface can be used in the thin slice high as above-mentioned gas block, either can be used and coats or be laminated with the agglutinative material of melting in inner wall and can be with thermosealed compound foil.Use the component of available cheap and good airproof performance, the solvent resistance high buffering discharge fluctuation of these compound foils.
Also, the gas to the component for being used in buffering fluctuation, uses the low gas of the permeability than oxygen, such as the available same effect such as nitrogen and argon.Additionally by and with gas barrier high sealing material and low-permeability gas, higher gas barrier can be played.
The preferred form of component as buffering discharge fluctuation of the invention is preferably following construction, increase as far as possible with the soaking area of masking liquid and obtain fluctuate buffering effect more effectively with lesser volume, and/or be set as will not generating the fold due to caused by compression or the shape of necking down to which secondary vibration will not be generated due to buffering the part distortion fluctuated.It is so-called herein to soak area, refer to the total of the area contacted in the state that the component of buffering discharge fluctuation is configured in coating unit with masking liquid.
Soak area is preferably the surface area of buffering fluctuation component 60% or more, more preferably 80% or more, most preferably 95% or more.Be set as the surface area of buffering fluctuation component by that will soak area 60% or more, can obtain the effect for more effectively fluctuating buffering with lesser volume.Area, surface area are soaked, the value when it is 25 DEG C that the pressure of masking liquid, which is 1 atmospheric pressure, temperature, is used.
In addition, above-mentioned buffering spues, the collapsibility Index A of the component of fluctuation indicated with following formula (1) is preferably 1.4 or more 20 or less.
A=S/ (4.84 × V2/3)……(1)
Here, S indicates that the component for buffering under 25 DEG C, 1 atmospheric pressure fluctuation and masking liquid soak area (cm2), V indicates the volume V (cm of the component of the buffering fluctuation under above-mentioned condition3)。
In the case where given volume, surface area is minimum when shape is ball.Because volume is V (cm3) ball surface area be 4.84 × V2/3, the collapsibility Index A that institute's above formula (1) indicates illustrates that above-mentioned buffering spues several times of the surface area for soaking the ball that area is same volume of component of fluctuation, and collapsibility Index A is bigger to indicate more flat.By making collapsibility 1.4 or more Index A, the buffering effect that particularly can be more effectively fluctuated with lesser volume, fold or necking down caused by will not generating due to compression, so as to inhibit the secondary vibration due to caused by the deformation of the component of buffering fluctuation.In addition, by for 20 hereinafter, can particularly become the good coating unit of discharge responsiveness.The collapsibility preferred range of Index A is 3 or more 10 or less.
Such as, when forming the component of above-mentioned buffering discharge fluctuation, 2 sheets are enclosed into the flat pattern for being bonded and being set as to seal peripheral part with material, such situation is compared with enclosing spherical situation for gas, available many times soak area, so becoming the excellent buffering fluctuation component of discharge responsiveness even if small in size, the also available enough fluctuation buffering effects for the gas being enclosed.In addition, for the component being configured in such a way that all surfaces and masking liquid contact in pipeline, although equably applying pressure from whole directions, but meet above formula (1) be substantially flat pattern component due to compress caused by deformation, only to the deformation of more flat shape.So, even if applying higher compression stress, fold or necking down are not easy to produce in the material of enclosed gas, so as to inhibit the delay of the volume change due to caused by fold or necking down and generate vibration, in addition, such shape, it can inhibit the deflection of material itself, there is the advantages of requirement characteristic of the mechanical characteristic of the material to enclosed gases such as resistance to bend(ing), plastic deformation stress, elastic restoring forces is lower, so that the selecting range of material is wide, so ideal.
But unlimitedly take collapsibility Index A greatly, it is not only difficult to configure into pipeline, and increase the volume of enclosed material only to also bring along view in the reduction of specific gravity, the substantive of the gas part for effectively working to fluctuation buffering soaks area and will not become larger.So collapsibility Index A should be 20 or less.In addition, the preferred good range of collapsibility Index A is 2 or more 10 or less.
In the component that buffering of the invention spues fluctuation, it is not particularly limited, can be suitably set according to the cymomotive force and required discharge responsiveness to be buffered as the volume sealed.The component of above-mentioned buffering discharge fluctuation can be adapted for the purposes for the gap coating for most paying attention to the discharge stability discharge responsiveness of pump.
Intermittent application use on the way, the discharge speed be low speed the case where it is more, as be suitable for such purpose pump, it can be cited for example that piston type quantitative pump.For discharge speed, it is size and these purposes such as coating speed according to the basis material as coating object and the numerical value designed, it is not particularly limited, but the component of buffering fluctuation of the invention, even being particularly 0.1~20cm in the discharge-amount Q per second of the masking liquid to spue from coating unit3Generated fluctuation in the extremely small pump of such discharge speed can also make to buffer small fluctuation and discharge responsiveness satisfactory to both parties.
When using the good pump of the device discharge stability as above-mentioned piston type quantitative pump, it is important that deteriorate discharge responsiveness and improve fluctuation buffering effect.In the case where such intermittent application, volume V (cm of the component of above-mentioned buffering discharge fluctuation under 25 DEG C, 1 atmospheric pressure3) and from coating unit spue masking liquid discharge-amount Q (cm per second3), preferably meet following formula (2).More preferably meet following formula (3).
0.05≤V/Q≤2      (2)
0.05≤V/Q≤0.5    (3)
By meeting above formula (2) and preferably meeting above formula (3), thus coating unit that particularly can be excellent as fluctuation buffering effect and discharge responsiveness.
As the preferred embodiment of coating unit of the invention, coating unit of the invention, another for preferably having other than painting liquid supplying device as shown in Figure 2 further increases the device 10 of pipeline internal pressure.The device for further increasing pipeline internal pressure, refers to that the pipeline internal pressure improved by painting liquid supplying device when the device is arranged is such device in 1.1 times of range above of the pipeline internal pressure when being not provided with the device.If in the component for the place configuration buffering discharge fluctuation for getting higher pipeline internal pressure using this device, even then small discharge fluctuates the pipeline internal pressure due to increasing, the responsiveness of the buffering as caused by the component can be improved, more effectively buffering fluctuation, even and the fluctuation of the negative pressure of moment generation, it can also be restored by the volume of the component to make to spue and stablize.As the device 10 for increase pipeline internal pressure, it can enumerate and a part of pipeline pipeline attenuates, or the methods of way setting throttle orifice or aperture adjustment valve in the duct.
In the present invention, pipeline internal pressure as the standard in coating unit is not particularly limited, if but according to the economy in engineering technology, the upper limit is preferably in 1MPa range below, in the case where the pump as using hydraulic pump for the purpose of the few quantitative interval discharge of the fluctuation that spues, even if lower internal pressure is it is also contemplated that have enough effects, as long as so being more preferably set as 0.5MPa or less in view of the leakproofness of piston and the work pressure of line changeover valve.It is not particularly limited as lower limit, if but the pressure for the component compresses for fluctuating buffering is not achieved in pipeline internal pressure, the buffering effect of pressure oscillation caused by volume changes cannot be then generated certainly, so even if being preferably also the internal pressure for being at least set as normal pressure or more in the case where the component using gas of buffering fluctuation.
In turn, with by configured in pressure sensor and the recording gauge etc. for pumping exhaust end, the device of the deterioration of the grasp component that the rising gradient of raised pipeline internal pressure, detection buffering fluctuate gradually later since spuing just, it is checked it is possible thereby to be used in and sound an alarm promotion, or stops the supply etc. of pump.
Embodiments described above is only the mode of an implementation, there can be various change in the range of not damaging main points of the invention, the present invention is not limited to above-mentioned specific embodiment, can be applied to require all fields such as the various display equipment of uniform intermittent application, display equipment colour filter, optical light filter.
Such as, in the manufacturing process for being used in colour filter, implement all or part of RGB (red, green, blue) each pixel or the black matrix being present between pixel and covering coat using coating unit of the invention, for pixel or black matrix, masking liquid itself can be made with photonasty or be coated with photonasty resist on again, and carry out pattern-forming using photoetching process.Obtained pattern carries out the processing of thermmohardening etc. as needed, in addition the process by forming the compositions such as electrode and alignment films, to become colour filter.It is same for LCD array, in addition to using coating unit or coating method of the invention that can also make by a conventionally known method to manufacture LCD array.
Embodiment
Embodiment is enumerated below and further illustrates the present invention, but the present invention is not limited to these embodiments.
(evaluation method)
A. oxygen permeability
It is measured under conditions of 40 DEG C of temperature, humidity 90%RH (relative humidity) according to Japanese Industrial Standards K 7129 (1999), the OX-TRAN2/20 manufactured using mono- Le society of モ ダ Application U Application ト ロ.
B. interference is uneven
The evaluation of uniformity as film, using the Na lamp of the single wavelength to dry coating surface illumination wavelength 589nm and with the method for visually observing its reflected light.The evaluation method is by using the light source of single wavelength to the reflected light interference from glass surface and film coated surface, even the film thickness of very small film, which changes, can be used as the uneven and evaluation method by visuognosis out of interference.
For along the distance (hereinafter referred to as coating distance) away from coating starting position seen toward coating direction in 30%~70% range from coating starting position to the distance of coating end position, see whether exist with the interference unevenness for the strip that the direction (direction parallel with nozzle) perpendicular to coating direction is longitudinal direction, with benchmark below judgement.
Excellent: interference unevenness is completely absent
It is good: it is uneven to there is very sparse interference
Qualified: it is uneven that there are sparse interference
Unqualified: it is uneven that there are dense interference
When interference is uneven unqualified, in the case where being used in the coloring layer of colour filter, when with having used the LCD panel of thin film transistor base plate to be bonded for the display monitor, there is gradation unequal in picture, cannot use.In addition in the case where the coating of the alignment films in the protective film for colour filter or when padding the coating of column, making LCD panel, because the gap unevenness that can become LCD liquid crystal layer is uneven with orientation, make the deterioration of the display monitor, so cannot use.
C. average film thickness, coating stabilizing distance, film thickness distribution width
Using the contact film thickness gauge (device name: MCPD-2000) of big tomb electronics, in the range of coating distance 2mm~450mm, with the film thickness in the Central Line of the measuring space coating width of 2mm.
A. average film thickness
Using the average value of the film thickness of the range (normal coated portion) of coating distance 400mm~450mm as average film thickness.
B. film thickness distribution width
Using the difference of the maximum value of the film thickness in the range (normal coated portion) of coating distance 400mm~450mm and minimum value as film thickness distribution width R, with following benchmark evaluations.
Excellent: film thickness distribution width R is at 0.005 μm or less
Good: film thickness distribution width R is than 0.005 μm greatly and at 0.01 μm or less
Qualified: film thickness distribution width R is than 0.01 μm greatly and at 0.03 μm or less
Unqualified: film thickness distribution width R is bigger than 0.03 μm
Film thickness distribution width R is the smaller the better, and in the case where 0.03 μm or more, in the coloring layer for being used in colour filter, becoming the display monitor with the bonding of thin film transistor for liquid crystal display device liquid crystal board then becomes the gradation unequal of picture, cannot use.
In addition, the gap for becoming the liquid crystal layer of liquid crystal display device is uneven, makes the deterioration of the display monitor, so cannot use in the case where being used for the protective film of colour filter and the coating of liner column.
C. stabilizing distance is coated
The distance away from coating starting point of the point except ± 0.5% range of above-mentioned average film thickness will be finally reached since coating distance 2mm when from coating the direction that becomes larger of distance sequentially, and be set as coating stabilizing distance, with following benchmark evaluations,
Excellent: coating stabilizing distance is in 10mm or less
Good: coating stabilizing distance ratio 10mm is big and in 15mm or less
Qualified: coating stabilizing distance ratio 15mm is big and in 20mm or less
Unqualified: coating stabilizing distance ratio 20mm is big, or there are the points outside the range of above-mentioned average film thickness ± 0.5% in range of the coating distance greater than 50mm.
It is the smaller the better to coat stabilizing distance, in 20mm or more, especially becomes underproof region in a basis material on the way in the use of intermittent application and increases, so problematic in use.
D. performance is used continuously
It is continuously coated on 1000 sheet glass substrates, the interference unevenness for carrying out above-mentioned A to the film of the 500th, the 1000th is evaluated, with benchmark below judgement.
Excellent: the interference of the 1000th film is not excellent
Good: the interference of the 1000th film is not good or qualified
Qualified: the interference of the 500th film is not excellent, good or qualified, and the interference of the 1000th film is unqualified
Unqualified: the interference unevenness of the 500th and the 1000th film is all unqualified
(embodiment 1)
Fig. 1 shows the infusion flow charts of the slit die mode coating unit as the coating unit used in the present embodiment.It uses the piston type hydraulic pumps 3 of internal diameter 18mm as liquid supplying device is applied, uses discharge slit width 620mm, 100 μm of slit gap of die nozzle 6 as coating unit.In addition, room 5 is set on pipeline, the buffering of the enclosed construction for strongly eliminating masking liquid stagnant portions in the room 5 spues the component of fluctuation, spues the component 5a of fluctuation as buffering, using by by 2 20 × 20mm of size, thick 100 μm of (oxygen permeabilities: 800cm3/m2DayMPa polyethylene sheets) are bonded and heat seal the width of the 2mm of peripheral part, to enclose 0.8cm3Air component.0.091 times regarded in specific gravity as the actual density of the material of enclosed gas of the component, soaks 100% that area is surface area, collapsibility Index A=1.84, V/Q=0.343.Use this coating unit, 620 × 750mm, thickness 0.7mm without on alkaline glass substrate, coating is using diethylene glycol dimethyl ether as acrylic ester clear polymer solution (light liner acrylate polymer) that solvent, solid component are 16 weight %.
Herein, as the preparation in advance before coating, masking liquid is put into from painting flow container first, (1) Attractive side switching valve 2 is opened, (2) attract masking liquid with hydraulic pump 3, (3) Attractive side switching valve 2 is closed, (4) exhaust end switching valve 4 is opened, (5) 3 discharge masking liquid of hydraulic pump is used, (6) exhaust end switching valve 4 is closed, the circulation for implementing above (1)~(6), until until coating tank to the gas-liquid in the masking liquid pipeline of die nozzle is replaced and fully completed.
In the state of entirely eliminated the residual bubble in masking liquid pipeline, attract 20.76cm with hydraulic pump 3 after opening Attractive side switching valve 23Masking liquid, the short side side end of basis material 7 (glass substrate) for being fixed on die nozzle 6 on workbench 8 close to absorption reaches 100 μm, with masking liquid discharge speed 2.563cm3/ the second starts the discharge of hydraulic pump 3.It is formed after masking liquid pearl between the front end and glass substrate 7 of gap nozzle 6, while the discharge for continuing the state, makes the mobile 750mm of workbench 8 to form uniform coating on 7 overall surface of glass substrate of 620 × 750mm with 6m/ seconds speed.In addition, making from the pipeline internal pressure 0.01MPa (the pipeline crushing only generated in masking liquid path kind) for applying liquid supplying device to coating unit.
Substrate after coating puts into vacuum chamber at once and is dried in vacuo, and is then hardened 10 minutes in heating board-like hardening furnace with 90 DEG C of dryings, to obtain 3.73 μm of average film thickness of dry coating.Evaluation result is indicated in table 1.
(table 1)
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 5
The component of buffering discharge fluctuation Gas (volume) Air (0.8cm3) Air (0.8cm3) Air (0.8cm3) Air (0.7cm3)
The material of enclosed gas Polyethylene Polyethylene Gas barrier thin slice Gas barrier thin slice
Depending in specific gravity/material actual specific gravity   0.091   0.091   0.107   0.194
Soak ratio (%) of the area relative to surface area   100   100   100   100
Collapsibility Index A   1.84   1.84   1.82   3.46
Oxygen permeability (the cm of the material of enclosed gas3/m2·day·MPa)   800   800   5   5
Make pipeline internal pressure further raised device (internal pressure) Nothing Needle valve (0.1MPa) Needle valve (0.1MPa) Needle valve (0.1MPa)
  V/Q   0.343   0.343   0.350   0.339
Interfere uneven (observation of Na lamp) It is qualified It is excellent It is excellent It is excellent
Film thickness distribution width Qualified (0.012 μm) Excellent (0.004 μm) Excellent (0.004 μm) Excellent (0.004 μm)
Coat stabilizing distance Good (12mm) Good (14mm) Good (14mm) Excellent (10mm)
Performance is used continuously It is good It is qualified It is excellent It is excellent
A. interference is uneven
It can be confirmed uneven with the interference for the sheet shape that the direction (with nozzle parallel direction) vertical with coating direction is longitudinal direction.The interference unevenness of the strip is due to caused by small film thickness unevenness, and the film thickness unevenness is due to when making movable workbench while from gap nozzle discharge masking liquid and carrying out film formation, vibrate masking liquid pearl because the discharge speed from die nozzle knifeedge changes, thus caused by making to change to the liquid buildup amount of glass substrate.Resulting substrate in the present embodiment, because being that sparse strip is uneven by visuognosis, it is believed that qualified.
B. average film thickness, coating stabilizing distance, film thickness distribution width
Average film thickness in the present embodiment is 3.73 μm, and being judged to coating stable range of value is 3.71~3.75.Coating stabilizing distance is 12mm, is judged as good (Fig. 5-a).
C. performance is used continuously
Because the 1000th interference unevenness is evaluated as qualification, it is determined that being good.
(embodiment 2)
Flow chart as shown in Figure 2, needle valve is set as the device 10 for increase pipeline internal pressure, valve opening is adjusted until measuring the indicated value of the pressure gauge 9 of the pipeline pressure between painting liquid supplying device and the needle valve as 0.1MPa, film is carried out similarly to Example 1 later and is formed.
Evaluation result indicates in table 1.
A. interference is uneven
The interference unevenness of strip be can't see completely, so being judged as excellent.
B. average film thickness, coating stabilizing distance, film thickness distribution width
Coating stabilizing distance is that 14mm is judged as good (Fig. 5-c).
In stablizing coating range, R=0.004 μm of film thickness distribution width is compared with embodiment 1, is significantly improved, and is determined as excellent (Fig. 5-d).
C. performance is used continuously
500th interference unevenness is evaluated as qualification, and the 1000th is unqualified, so continuous use performance is judged as qualified.
In addition, completing the volume of the air bag after 1000 coatings with graduated cylinder measurement, the volume of the air bag containing sealing material was from about 0.9cm originally3It is reduced to about 0.6cm3。
It can speculate that enclosed air penetration is crossed gradually flows out as the polyethylene of bag material due to increasing pipe internal pressure with needle valve.
(embodiment 3)
Flow chart as shown in Figure 2, with 20 × 20mm of size, 112 μm of thickness of gas barrier thin slice (Mitsubishi Gas Chemical P Co., Ltd. TS bags: 5cm3/m2DayMPa), the material as the enclosed gas of the component 5a of buffering discharge fluctuation, in addition to this carries out film in the same manner as in Example 2 and is formed.0.107 times regarded in specific gravity as the actual density of the material of enclosed gas of the component, soaks 100% that area ratio is surface area, collapsibility Index A=1.82, V/Q=0.350.
Evaluation result indicates in table 1.
A. interference is uneven
Strip unevenness be can't see completely, be determined as excellent.
B. average film thickness, coating stabilizing distance, film thickness distribution width
Coating stabilizing distance is 14mm, is judged as good.
In stablizing coating range, film thickness distribution width is R=0.004 μm, is judged as excellent.
C. performance is used continuously
500th, the 1000th evaluation be all completely invisible interference it is uneven thus be it is excellent, continuous use performance is judged as excellent.
The volume of the air bag of 1000 coatings is completed with graduated cylinder measurement, the volume of the component of buffering discharge fluctuation is about 0.9cm3, almost do not see variation.
It has been confirmed that the material high by using gas barrier, can be significantly increased the continuous use performance of the component of buffering discharge fluctuation.
(embodiment 4)
The method of the deterioration of the component for the fluctuation that spues is buffered as detection, flow chart as shown in Figure 2, it is constituted using following, i.e., when control unit sequence controller 11 sends discharge commencing signal C1 to hydraulic fluid motor drive circuit 12, the pipeline internal pressure risen with the measurement of pressure gauge 9 with the discharge beginning of hydraulic pump, at the time of pipeline internal pressure reaches setting pressure (0.095MPa), to 11 output pressure arriving signal S1 of control unit sequence controller.At this moment slave C1 is output to the internal timer measurement of the time control unit sequence controller 11 until S1 input.
Other than the device of the rising movement of setting said determination pipeline internal pressure, in the same manner as in Example 2, and then the arrival time of the pipeline internal pressure after continuous coating starts is about 0.9 second, pressure arrival time at the time of completing 200 is about 0.85 second, pressure arrival time at the time of completing 500 coatings is about 0.8 second, pressure arrival time at the time of completing 1000 coatings is about 0.6 second, has the tendency that such shortening.The result of the volume of fluctuation absorption component is measured it can be identified that volume reduces 0.3cm at the time of completing 1000 coatings3, it is possible to confirmation can detect the deterioration of the component of buffering fluctuation with the rising gradient of pipeline internal pressure.
(embodiment 5)
For the purpose of further increasing discharge responsiveness, make the volume 0.7cm of enclosed gas3, sealing shape is 25 × 30mm, in addition to this carries out film similarly to Example 3 and is formed.0.194 times regarded in specific gravity as the actual density of the material of enclosed gas of the component of buffering discharge fluctuation, soaks 100% that area is surface area, collapsibility Index A=3.46, V/Q=0.339.Evaluation result indicates in table 2.
A. interference is uneven
In the reflective observing using Na lamp of dry coating, it can't see strip unevenness completely, be judged as excellent.
B. average film thickness, coating stabilizing distance, film thickness distribution width
Coating stabilizing distance is 10mm, is judged as excellent (Fig. 6-a).
In stablizing coating range, film thickness distribution width is R=0.004 μm, is judged as excellent (Fig. 6-b).
C. performance is used continuously
500th, the 1000th evaluation be all that can't see interference completely uneven, so continuous use performance is judged as excellent.
The air bag volume of 1000 coatings is completed with graduated cylinder measurement, the air bag volume containing sealing material is about 0.8cm3, it is hardly visible variation.
The state of the air bag in the pipeline under coating state is configured at visual confirmation, even the deformation in compressive state is also pressed into be flat, so folding line and fold all be can't see in thin slice, it is good.
(embodiment 6)
As the component of buffering discharge fluctuation, silicone tubing (the oxygen permeability 5000cm in outer diameter 6mm, internal diameter 4mm is used3/m2DayMPa or more) both ends cap and in the enclosed about 0.68cm in inside3Air component, carry out film forming in the same manner as in Example 5.0.6 times regarded in specific gravity as the actual density of the material of enclosed gas of the component, soaks 100% that area is surface area, collapsibility Index A=1.97, V/Q=0.662.Evaluation result indicates in table 1.Interference is not qualification, and coating stabilizing distance is 17mm (qualification).In addition film thickness distribution width is R=0.016 μm (qualification).It is qualification that performance, which is used continuously,.
(embodiment 7)
Component as buffering discharge fluctuation, the 2mm width at the both ends of the component of buffering discharge fluctuation used in embodiment 5 is fixed on enclosed wall surface of the container, as the component for the state for having one side not contact with liquid using with accessory, carries out film forming in the same manner as in Example 5.0.113 times regarded in specific gravity as the actual density of the material of enclosed gas of the component, soaks 40% that area is surface area, collapsibility Index A=1.73, V/Q=0.339.Evaluation result indicates in table 2.Interference is not qualification, and coating stabilizing distance is 12mm (good), and film thickness distribution width is R=0.016 μm (qualification).In addition, continuous use performance is excellent.
(table 2)
Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9
The component of buffering discharge fluctuation Gas (volume) Air (0.68cm3) Air (0.7cm3) Air (0.7cm3) Air (0.7cm3)
The material of enclosed gas Silicone tubing Gas barrier thin slice Gas barrier thin slice Gas barrier thin slice
Depending in specific gravity/material actual specific gravity   0.600   0.113   0.067   0.672
Soak ratio (%) of the area relative to surface area   100   40   100   100
Collapsibility Index A   1.97   1.73   1.16   16.0
Oxygen permeability (the cm of the material of enclosed gas3/m2·day·MPa) 5000 or more   5   5   5
Make pipeline internal pressure further raised device (internal pressure) Needle valve (0.1MPa) Needle valve (0.1MPa) Needle valve (0.1MPa) Needle valve (0.1MPa)
  V/Q   0.662   0.339   0.832   0.832
Interfere uneven (observation of Na lamp) It is qualified It is qualified It is good It is good
Film thickness distribution width Qualified (0.016 μm) Qualified (0.016 μm) Good (0.010 μm) Good (0.008 μm)
Coat stabilizing distance Qualified (17mm) Good (12mm) Good (12mm) Qualified (16mm)
Performance is used continuously It is qualified It is good It is good It is good
(embodiment 8)
As the component of buffering discharge fluctuation, it is bonded and by the 2mm width of peripheral part heat seal using by 2 15 × 15mm of size, 112 μm of thickness of gas barrier thin slice (TS bags of Mitsubishi Gas Chemical P Co., Ltd.) in internal enclosed 0.7cm3Air component, carry out film in the same manner as in Example 5 and formed.0.067 times regarded in specific gravity as the actual density of the material of enclosed gas of the component, soaks 100% that area is surface area, collapsibility Index A=1.16, V/Q=0.832.Evaluation result indicates in table 2.It is not good for interfering, and coating stabilizing distance is 12mm (good), and film thickness distribution width is R=0.010 μm (good).In addition, continuous use performance is good.
(embodiment 9)
It spues the component of fluctuation as buffering, using 2 80 × 80mm of size, 112 μm of thickness of gas barrier thin slice (TS bag of Mitsubishi Gas Chemical P Co., Ltd.) are bonded and heat seal the 2mm width of peripheral part to enclose 0.7cm internal3Air component, carry out film in the same manner as in Example 5 and formed.0.672 times regarded in specific gravity as the actual density of the material of enclosed gas of the component, soaking area is the 100% of surface area, collapsibility Index A=16.0, V/Q=0.832.Evaluation result indicates in table 2.It is not good for interfering, and coating stabilizing distance is 16mm (qualification), and film thickness distribution width is R=0.008 μm (good).In addition, continuous use performance is good.
(comparative example 1)
Flow chart as shown in Figure 3 is carried out film in the same manner as in Example 1 and is formed in addition to the component for the fluctuation that do not spued using buffering.Evaluation result indicates in table 3.Interference is not unqualified.
Since there is no the buffer unit for generating discharge operating lag, the disorder of film thickness in the zonule of coating distance tails off (Fig. 7-a), but even if point outside range after coating distance 50mm there are still average film thickness ± 0.5%, so being judged as unqualified.Film thickness distribution width is R=0.041 μm (Fig. 7-b, unqualified).
In addition, the 500th, the interference unevenness of the 1000th film be all unqualified, so continuous use performance is judged as unqualified.
(table 3)
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
The component of buffering discharge fluctuation Gas (volume) Nothing Air (5cm3) Air (1cm3) Without (silicone foam rubber)
The material of enclosed gas Nothing Nothing
Depending in specific gravity/material actual specific gravity   -   -   -   0.5
Soak ratio (%) of the area relative to surface area   -   -   -   100
Collapsibility Index A   -   -   -   5.67
Oxygen permeability (the cm of the material of enclosed gas3/m2·day·MPa)   -   -   -   -
Make pipeline internal pressure further raised device (internal pressure) Nothing Nothing Nothing Nothing
  V/Q   0   1.951   0.390   1.249
Interfere uneven (observation of Na lamp) It is unqualified It is good It is qualified It is qualified
Film thickness distribution width Unqualified (0.041 μm) Good (0.010 μm) Qualified (0.017 μm) Qualified (0.016 μm)
Coat stabilizing distance Unqualified (> 50mm) Unqualified (22mm) Good (14mm) Good (12mm)
Performance is used continuously It is unqualified It is good It is unqualified It is unqualified
(comparative example 2)
Flow chart as shown in Figure 4 uses air cell type accumulator (volume 50cm except the buffer unit without using buffering discharge fluctuation3, airtight amount 5cm3) other than, film is carried out in the same manner as in Example 1 to be formed.Evaluation result indicates in table 3.Interference be not it is good, coating stabilizing distance is 22mm (Fig. 7-c, unqualified), and film thickness distribution width is R=0.010 μm (Fig. 7-d, good).In addition, the 500th, the interference unevenness of the 1000th film be all good, so continuous use performance is judged as good.
Without using the material of enclosed gas, and the air cell type accumulator that gas is directly configured in masking liquid is used, so the available effect to a certain degree in the uneven attenuating of interference, but it is not able to satisfy discharge responsiveness.
(comparative example 3)
Air cell type accumulator (volume 50cm is used in addition to the component without using buffering discharge fluctuation3, airtight amount 1cm3) other than, film is carried out in the same manner as in Example 1 to be formed.Evaluation result indicates in table 3.Interference is not qualification, and coating stabilizing distance is 14mm (Fig. 8-a, good), and film thickness distribution width is R=0.017 μm (Fig. 8-b, qualified), and continuous use performance is unqualified.
(comparative example 4)
It is configured at the foaming body of the silicone rubber of 40 × 40mm of size, thickness 6mm as the spue component of fluctuation of buffering and is formed using in pipeline liquid, in addition to this carrying out film in the same manner as in Example 1.Evaluation result indicates in table 3.Due to not using being configured to air seal in internal component, so interference is not qualification, coating stabilizing distance is 12mm (Fig. 8-c, good), and film thickness distribution width is R=0.016 μm (Fig. 8-d, qualification).In addition, continuous use performance is unqualified.
(embodiment 10, comparative example 5)
Colour filter and LCD panel using present invention production with light liner column.
(production of colour filter)
(production of resin black matrix) is using n-methyl-2-pyrrolidone as solvent, make 3,3 ', 4,4 '-biphenyltetracarboxylic acid dianhydrides, 4,4 '-diamino-diphenyl ethers and the reaction of bis- (3- aminopropyl) tetramethyl disiloxanes, obtain polyimide precursor (polyamic acid) solution.It will be dispersed 30 minutes with following carbon black comminuting matters formed with homogenizer with 7000rpm, filter glass pearl modulates black wash.Carbon black comminuting matter carbon black (MA100, Mitsubishi's chemical conversion (strain) system): 4.6 parts, polyimide precursor solution: 24.0 parts, N-Methyl pyrrolidone: 61.4 parts, bead: 90.0 parts, it is coated with black wash with rotator on alkali-free glass (Japanese electric apparatus glass (strain) system, OA-2) substrate of 300 × 350mm size, with 135 DEG C of progress, 20 minutes semi-solid preparations in drying machine.Then, it is coated with positive-workingresist (Shipley Microposit (registered trademark) RC100 30cp) with rotator, it is 10 minutes dry at 90 DEG C.Resist film thickness is 1.5 μm.The exposure machine PLA-501F made with Canon (strain), across with black matrix portion, architrave portion, the voice-over structure of a part (basal part) of column photomask, be exposed.Next, 23 DEG C of aqueous solution of the tetramethylammonium hydroxide (TMAH) containing 2 weight % is used for developer solution, substrate is impregnated in developer solution, swing substrate in a manner of in 10cm amplitude every five seconds round-trip 1 time simultaneously, to carry out the development of positive-workingresist and the corrosion of polyimide precursor simultaneously.Developing time is 60 seconds.Later, remove positive-workingresist with methylcellosolve acetate, also, carry out at 300 DEG C solidification in 30 minutes, obtain black matrix portion, architrave portion, basal part structure resin black matrix substrate.The film thickness of resin black matrix substrate is 0.90 μm, and OD value is 3.0.In addition, the reflectivity (Y value) on the interface of resin black matrix and glass substrate is 1.2%.About 50000 μm of the area of the substrate for the column that resin black matrix outside by picture is constituted2.The pedestal of column is also formed in the region being cut off when becoming the liquid crystal display device outside picture.Every about 1cm2One ratio equally spaced periodically configures.
(production of coloring layer)
Then, prepare the bi-anthraquinone based dye indicated with Color index No.65300 Pigment Red 177, the phthalocyanine green based dye indicated with Color Index No.74265 Pigment Green 36, the phthalocyanine blue based dye indicated with Color Index No.74160 Pigment Blue 15-4, the dyestuff as red, green, blue respectively.Above-mentioned dyestuff is mixed into dispersion respectively in polyimide precursor solution, obtain three types of red, green, blue mill base.
Firstly, being coated with blue slurry, heated-air drying 10 minutes at 80 DEG C, semi-solid preparation 20 minutes at 120 DEG C on substrate.Later, 20 minutes dry at 80 DEG C after being coated with positive-workingresist (Shipley Microposit (registered trademark) SRC100 30cp) with rotator.With mask exposure, substrate is immersed in alkaline-based developer (Shipley Microposit (registered trademark) 351), and shakes substrate on one side, carries out the development of positive-workingresist and the corrosion of polyimide precursor simultaneously on one side.Later, positive-workingresist is removed with methylcellosolve acetate, and solidify within 30 minutes at 300 DEG C.The film thickness in colored pixels portion is 1.7 μm.Using the pattern-forming, the substrate that the coloring layer of blue is re-formed in blue pixel and the substrate of black matrix voice-over is formed.The area of the substrate of the coloring layer of blue outside picture is about 25000 μm2, the area of the substrate of the coloring layer of the blue in architrave is about 500 μm2。
After washing, similarly, the formation of red pixel is carried out.The substrate of column is not re-formed.
The film thickness in red pixel portion is 1.8 μm.
And then after washing, it is identically formed green pixel.The substrate of column is not formed.The film thickness in green pixel portion is 1.5 μm.
(production of light liner column)
Use photosensitive JSR minus acrylate based material (NN810 or NN700) as column material, the coating unit of embodiment 5 is used in embodiment 10, the coating unit that comparative example 1 is used in comparative example 5, forms on substrate in above-mentioned coloring layer be coated in the same manner as in Example 5.
Substrate after coating is put into immediately after vacuum chamber is dried in vacuo, and is carried out dry hardening in 10 minutes at 90 DEG C in heating board-like hardening furnace, be can't see 3.73 μm of average film thickness uneven of dry coating of interference completely.
Then 200mJ/cm is irradiated with exposure machine (Canon PLA-501F)2(i line) is masked exposure.Substrate is immersed in TMAH aqueous solution (0.15%), and while shaking substrate while carrying out developing pattern forming.Column is formed in picture in the substrate of the black matrix in architrave, outside picture using the pattern-forming, drying is hardened 20 minutes at 279 DEG C in heating board-like hardening furnace later.
About 110 μm of the upper surface of column of resin in picture product2, about 120 μm of product below resin layer2.It is about 110 μm that upper area is similarly formed as in architrave2, lower area is about 120 μm2.About 10000 μm of the upper surface of column of resin outside picture product2(100 × 100 μm of size), about 12000 μm of product below resin layer2(110 × 110 μm of size).Pillar height degree is 3.1 μm.Also, the column in picture is with every 3 pixel (1 pixel: 100 300 μm of μ ms) 1 ratio setting.
When the colour filter with halogen lamp illumination observation with light liner column, although the fluctuation of pillar height degree is seen as reflection unevenness, but the colour filter with light liner column being coated with the coating unit of embodiment 10, unevenness is reflected caused by can't see the height unevenness padded due to light, extremely well.On the other hand, the colour filter with light liner column being coated with the coating unit of comparative example 5, it can be seen that strong reflection caused by the height unevenness padded due to light is uneven, with low quality.
(embodiment 11)
The alignment films of polyimides system are arranged in (production of color liquid crystal plate body) on the colour filter of embodiment 10, implement orientation process.In addition, opposite substrate of the production with the transparent electrode with thin-film transistor element, is similarly arranged polyimides system alignment films, implement orientation process.It is bonded the colour filter of alignment films is provided with the transparent electrode substrate with thin-film transistor element with sealant, then cuts away the unwanted range outside picture.Then, liquid crystal is injected from the inlet for being set to sealing.Liquid crystal is injected to, and after placing ghost decompression, inlet is impregnated in liquid crystal groove, is carried out by restoring normal pressure.It injects after liquid crystal, seals inlet, and polarizer is fitted in into the outside of substrate to be fabricated to unit.Obtained liquid crystal plate body, which pads column by the light of no height unevenness, may insure uniform cell gap, to there is good display quality.
Technology of the invention is, in the coating unit that masking liquid is applied to basis material, in the case where the uniformity of the discharge fluctuations compromise film caused by vibration due to infusion pump etc., realizes that uniform film is formed by lowering discharge fluctuation.Especially in the field of display body purposes, even can also be found as display unevenness by vision since extremely small film thickness changes, to be affected to quality, so coating unit of the invention can be adapted for the film coating techniques of these display equipment.

Claims (15)

1. a kind of coating unit, it is that at least have the coating unit for applying liquid supplying device and masking liquid being coated on to basis material, they are connected by transfer line, masking liquid is coated on to the coating unit of basis material, it is characterized in that, being reached anywhere in the pressure generated by the painting liquid supplying device, the component of configuration buffering discharge fluctuation, the component of above-mentioned buffering fluctuation is at least by enclosing internal gas and enclosing the component that the material of the gas constitutes.
2. coating unit as described in claim 1, which is characterized in that above-mentioned buffering spue fluctuation component the actual specific gravity for regarding the material in specific gravity relative to above-mentioned enclosed gas as half below.
3. coating unit as claimed in claim 1 or 2, which is characterized in that 60% or more of the surface area for soaking the component that area is buffering discharge fluctuation of the component of above-mentioned buffering discharge fluctuation.
4. coating unit according to any one of claims 1 to 3, which is characterized in that the collapsibility Index A represented by following formula (1) of the component of above-mentioned buffering discharge fluctuation, below 1.4 or more 20；
A=S/ (4.84 × V2/3)        (1)
Wherein, what S indicated the component of the above-mentioned buffering fluctuation under 25 DEG C, 1 atmospheric pressure soaks area (cm with masking liquid2), V indicates the volume V (cm of the component of above-mentioned buffering fluctuation under the above conditions3)。
5. coating unit as described in any one of claims 1 to 4, which is characterized in that 40 DEG C of the material of above-mentioned enclosed gas, the oxygen permeability under conditions of 90%RH be 2500cm3/m2DayMPa or less.
6. such as coating unit according to any one of claims 1 to 5, which is characterized in that used as the method that masking liquid is coated on to basis material and use mold cladding process.
7. such as coating unit according to any one of claims 1 to 6, which is characterized in that there is the device for further increasing the pipeline internal pressure generated by painting liquid supplying device, pipeline internal pressure by the arrangement increases section configure the component that above-mentioned buffering fluctuates.
8. such as coating unit according to any one of claims 1 to 7, which is characterized in that at least pumped using piston type quantitative as liquid supplying device is applied.
9. coating unit as claimed in claim 8, which is characterized in that the discharge-amount Q per second of the masking liquid to spue from coating unit is 0.1~20cm3。
10. coating unit as claimed in claim 8 or 9, which is characterized in that above-mentioned buffering spues 25 DEG C of component of fluctuation, the volume V (cm under 1 atmospheric pressure3) and from coating unit spue masking liquid discharge-amount Q (cm per second3) meet following formula (2)
0.05≤V/Q≤2        (2)。
11. the coating unit as described in any one of claim 8~10, which is characterized in that the rising movement of pipeline internal pressure when measurement discharge starts.
12. masking liquid is coated on basis material using coating unit described in any one of claim 1~11 by a kind of coating method.
13. a kind of manufacturing method of colour filter, the process including using coating method described in claim 12 to be coated.
14. a kind of manufacturing method of LCD array substrate, the process including using coating method described in claim 12 to be coated.
15. a kind of display equipment, which is characterized in that use and utilize the obtained colour filter of method or LCD array substrate described in claim 13 or 14.
CN200580009576.3A 2004-03-25 2005-03-17 Painting device, painting method, and display member provided therefrom Pending CN1933920A (en)

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